Material having various functional group with high refractive index and method for preparing the same

Abstract

To provide monomers for optical resins for manufacturing optical resins with a high refractive index that can be used as an alternative to glass.SOLUTION: There is provided a new compound with a high refractive index of 1.7 or more, which has a fluorene and xanthene-based complex cardo structure expressed by the following formula. The compound of this invention can be applied to the manufacture of high refractive index optical resins. The fluorene and xanthene-based complex cardo structure of this compound has a high glass transition temperature (Tg) with the mobility of the molecular chain suppressed to the greatest extent possible. Therefore, it can also be used widely in the manufacture of high-heat-resistant resins that require thermal stability.SELECTED DRAWING: None

Description

[Technical field]

[0001] This invention was made under the support of the Ministry of Trade, Industry and Energy of the Republic of Korea under project specific number 1415179963 and project number 20013223, the research management specialist organization for this project is the Korea Institute for Industrial Technology Assessment and Management, the research project name is "Material component technology development", the research topic name is "Development of thermoplastic optical resin with a refractive index of 1.65 or more and light-blocking agent with an optical density of 6.5 or more for optical lenses of smart devices", the project execution organization is Kuppo Chemical Co., Ltd., and the research period is from 2024.01.01 to 2024.12.31.

[0002] In addition, the present invention was made under the support of the Ministry of Trade, Industry and Energy of the Republic of Korea under project specific number 1415178757 and project number 20013794, the research management specialist organization for this project is the Korea Institute for Industrial Technology Assessment and Management, the research project name is the "Demonstration Project for Fostering Industrial Technology Base Centers," the research project name is the "Composite Material Simultaneous Design Industrial Technology Base Center," the project execution organization is the Sungkyugang University Industry-Academia Cooperation Foundation, and the research period is from 2024.01.01 to 2024.12.31.

[0003] The present invention claims priority to Korean Patent Application No. 10-2023-0072497, filed on June 5, 2023, the disclosure of which is incorporated herein by reference.

[0004] The present invention relates to a high refractive index material having various functional groups and a manufacturing method thereof. More specifically, the compound has a complex cardo structure of fluorene and xanthene, and relates to a high refractive index monomer that can be used for optical resins that require a refractive index of 1.7 or more. [Background technology]

[0005] Conventionally, in order to manufacture optical resins having a high refractive index that can replace glass, refractive index improving monomers such as those in the following structure have been used. However, most monomers have a refractive index of about 1.3 to 1.6, which limits their applicability to applications requiring a high refractive index.

[0006] [ka]

[0007] Therefore, there is a need to develop a new compound having a higher refractive index than existing commercially available optical resin monomers. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Korean Patent No. 10-2418855 Summary of the Invention [Problem to be solved by the invention]

[0009] The present inventors have made extensive research efforts to develop high refractive index materials having various functional groups. As a result, they have designed a composite cardo structure of fluorene, which has a high molar refractive index and a low birefringence, and xanthene, which has a high molar refractive index, and developed a novel monomer compound with a higher refractive index than existing commercial materials by introducing a heteroatom that provides synergy in improving the refractive index. Therefore, the object of the present invention is to provide a compound having the structure of the following chemical formula 1 and a method for producing the same:

[0010] [ka]

[0011] Here, X and R 1a , R 1b , R 2a , and R 2b represents a substituent; X is O, S, or SO2; k1 and k2 independently represent an integer of 0 to 4; and p1 and p2 independently represent an integer of 0 to 4 (with the proviso that p1+p2 is an integer of 1 to 8). [Means for solving the problem]

[0012] The present inventors have made extensive research efforts to develop high refractive index materials having various functional groups, and as a result, have produced a compound having the structure of the following Chemical Formula 1, thereby completing the present invention.

[0013] According to one aspect of the present invention, there is provided a compound having the chemical structure of Formula 1:

[0014] [ka]

[0015] Here, X, R 1a , R 1b , R 2a , and R 2b represents a substituent; X is O, S, or SO2; k1 and k2 independently represent an integer of 0 to 4; and p1 and p2 independently represent an integer of 0 to 4 (with the proviso that p1+p2 is an integer of 1 to 8).

[0016] R 2a , and R 2b are independently H, linear or branched C 1-10 Alkyl, linear or branched C 1-10 Alkoxy, C 1-10 Hydroxyalkoxy, C 1-10 Alkoxy(C 1-10 ) Alkoxy, Phenyl, C 1-10 Alkoxyphenyl, halogen, amino, C 1-5 Haloalkyl, C 1-5 Alkylamino, C 1-5 Dialkylamino, arylamino, diarylamine, aryl C 1-5 It represents an alkylamino or cyclic amino group.

[0017] On the other hand, this compound has a complex cardo structure of fluorene and xanthene, and is a high refractive index monomer that can be used for optical resins that require a refractive index of 1.7 or more.

[0018] As used herein, the term "cardo compound" refers to a compound having a structure with cyclic side groups in the molecular backbone. Cardo compounds have the structural feature of having bulky lateral groups in the polymer backbone, which provides severe rotational hindrance to the backbone, resulting in very high heat resistance (high glass transition temperature) as well as excellent processability.

[0019] In one embodiment of the present invention, R 2a and R 2b The substituent represented by is not particularly limited, but is generally H or an alkyl group. The alkyl group may be a C1 to C6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a t-butyl group (for example, 1-4 Examples of the R include alkyl groups, particularly methyl groups. 2a and R 2b may be different or the same. In addition, R 2a or R 2b The bonding positions (substitution positions) of are not particularly limited. The substitution numbers k1 and k2 are preferably 0 or 1. Moreover, the substitution numbers k1 and k2 may be different from each other or the same.

[0020] In one embodiment of the present invention, the compound represented by Formula 1 may be represented by any one of Formulas 1-1 to 1-4 below:

[0021] [ka]

[0022] Here, X and R 1a , R 1b , R2a , and R 2b The relevant conditions are as described above in Chemical Formula 1.

[0023] In one embodiment of the present invention, the R 1a and R 1b may each be selected from the substituents represented by the following chemical formulas 2-1 to 2-17:

[0024] [ka] JPEG2024174847000006.jpg249169JPEG2024174847000007.jpg157169

[0025] In one embodiment of the present invention, the substitution numbers p1 and p2 are each independently 0 or 1. In addition, the substitution numbers p1 and p2 may be different or the same.

[0026] In one embodiment of the present invention, the compound of the present invention has a chemical structure selected from the following formulas 3-1 to 3-16:

[0027] [ka] JPEG2024174847000009.jpg231169JPEG2024174847000010.jpg138169

[0028] In other embodiments of the present invention, X may be O.

[0029] In a specific embodiment of the present invention, when X is O, the compounds of the present invention are represented by the following formulas 4-1 to 4-12:

[0030] [ka] JPEG2024174847000012.jpg218169JPEG2024174847000013.jpg79169

[0031] In a specific embodiment of the present invention, when X is O, the compound of the present invention is represented by any one of the following formulas 4-13 to 4-18:

[0032] [ka]

[0033] In other embodiments of the present invention, X may be S.

[0034] In a specific embodiment of the present invention, when X is S, the compound of the present invention is represented by any one of the following formulas 5-1 to 5-9:

[0035] [ka] JPEG2024174847000016.jpg153169

[0036] In a specific embodiment of the present invention, when X is S, the compound of the present invention has a chemical structure represented by any one of the following formulas 5-10 to 5-13:

[0037] [ka]

[0038] In yet another embodiment of the present invention, X may be SO2.

[0039] In a specific embodiment of the present invention, when X is SO2, the compound of the present invention has a chemical structure represented by any one of the following formulas 6-1 to 6-5:

[0040] [ka]

[0041] In another embodiment of the present invention, when X is SO2, the compound of the present invention is represented by the following formula 6-6:

[0042] [ka]

[0043] According to another aspect of the present invention, the xanthene derivative compound of the present invention has four phenyl groups, and can improve or improve various properties including optical properties. Therefore, the xanthene derivative compound of the present invention may be usefully used as a resin component, an additive, etc. In addition, since the xanthene derivative compound of the present invention has multiple hydroxyl groups, when the hydroxyl groups are adjusted to one or more groups and a functional group is introduced to form a resin component, the properties of the resin can be efficiently improved.

[0044] In one embodiment of the present invention, the resin component may be (i) a resin containing a xanthene-based compound represented by Chemical Formula 1 of the present invention as a monomer, or (ii) a resin composed of the xanthene-based compound and a resin.

[0045] In one embodiment of the present invention, the resin constituting the resin component (said resin component (i) or (ii)) is not particularly limited, and may be a conventional thermoplastic resin or a thermosetting resin (or a photocurable resin). The resin constituting the resin component may be used alone or in combination of two or more kinds.

[0046] Examples of thermoplastic resins include olefin resins (polyethylene, polypropylene, polymethylpentene, amorphous polyolefin, etc.), halogen-containing vinyl resins (chlorine-containing resins such as polyvinyl chloride, fluorinated resins, etc.), acrylic resins, styrene resins (polystyrene, acrylonitrile-styrene resin, etc.), polycarbonate resins (bisphenol A polycarbonate, etc.), polyester resins (polyalkylene arylate resins such as polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate, polyarylate resins, liquid crystal polyesters, etc.), polyacetal resins, and polyamide resins (polyamide 6, polyamide 66, polyamide 46, polyamide 6T, etc.). , polyamide MXD, etc.), polyphenylene ether resins (modified polyphenylene ether, etc.), polysulfone resins (polysulfone, polyethersulfone, etc.), polyphenylene sulfide resins (polyphenylene sulfide, etc.), polyimide resins (polyetherimide, polyamideimide, polyaminobismaleimide, bismaleimide triazine resin, etc.), polyetherketone resins (polyetherketone, polyetheretherketone, etc.), thermoplastic elastomers (polyamide elastomers, polyester elastomers, polyurethane elastomers, polystyrene elastomers, polyolefin elastomers, polydiene elastomers, polyvinyl chloride elastomers, fluorine-based thermoplastic elastomers), etc. The thermoplastic resins can be used alone or in combination of two or more.

[0047] Examples of the thermosetting resin include phenol resin, amino resin (urea resin, melamine resin, etc.), furan resin, unsaturated polyester resin, epoxy resin, thermosetting polyurethane resin, silicone resin, thermosetting polyimide resin, diallyl phthalate resin, vinyl ester resin (resin obtained by reacting epoxy resin with (meth)acrylic acid or its derivative, resin obtained by reacting polyhydric phenols with glycidyl (meth)acrylate, etc.). Thermosetting resins (or photocurable resins) also include polyfunctional (meth)acrylates, vinyl ethers (divinyl ether obtained by reacting a diol component with acetylene, etc.). The thermosetting resins can be used alone or in combination of two or more.

[0048] In addition, the thermosetting resin may contain an initiator, a reactive diluent, a curing agent, a curing accelerator, etc., depending on the type of thermosetting resin (or photocurable resin). For example, the resin composition containing the epoxy resin or urethane resin may contain an amine curing agent, etc., and the resin composition containing the unsaturated polyester resin or vinyl ester resin may contain an initiator (peroxide, etc.), a polymerizable monomer (reactive diluent such as (meth)acrylic acid ester or styrene), etc.

[0049] The resin component (i) or resin component (ii) of the present invention can be used alone or in combination of two or more kinds.

[0050] The resin component (i) contained as the constituent (monomer component) may have a resin skeleton composed of a xanthene derivative compound, and may be prepared by using a xanthene derivative compound corresponding to this polymerization component (or monomer component) as a polymerization component or constituent (e.g., a polyol component such as a diol component) of the resin. For example, in a resin (polyester resin, polyurethane resin, epoxy resin, vinyl ester resin, epoxy resin, polyfunctional (meth)acrylate, (poly)urethane (meth)acrylate, (poly)ester (meth)acrylate, vinyl ether, etc.) that uses a polyol component (particularly, a diol component) as a polymerization component or constituent, the xanthene derivative compound may be used in part or all of the polyol component.

[0051] In the resin component (i), the xanthene derivative compounds can be used alone or in combination of two or more as polymerization components (or constituents).

[0052] Resins (or resin components) constituting the preferred resin component include polyester resins, polyurethane resins (thermoplastic or thermosetting polyurethane resins), polycarbonate resins, acrylic resins [including thermosetting or photocurable resins such as polyfunctional (meth)acrylates], epoxy resins, vinyl ethers, etc. Also preferred are resins (thermoplastic resins) containing aromatic rings (benzene rings), such as aromatic polycarbonate resins (bisphenol A polycarbonate, etc.), polyester resins [polyalkylene arylate resins; polyarylate resins using aromatic dicarboxylic acids (terephthalic acid, etc.) and aromatic diols (biphenol, bisphenol A, xylene glycol, alkylene oxide adducts thereof, etc.) as polymerization components, etc.], polysulfone resins (polysulfone, polyethersulfone, etc.), polyphenylene sulfide resins (polyphenylene sulfide, etc.), etc.

[0053] In the following, a representative resin (or resin component) will be described in detail, specifically a resin (or resin component (i)) containing a xanthene derivative compound represented by the above chemical formula 1 as a monomer component (polymerization component, constituent component, copolymerization component).

[0054] (1) Polyester resin A polyester-based resin containing the xanthene derivative compound as a polymerization component (particularly a polyester-based resin polymerized with the xanthene derivative compound (generally a compound where p1 = p2 = 1) as a monomer component of the resin) can be obtained by reacting at least the xanthene derivative compound with a dicarboxylic acid component, and the polyester-based resin includes not only saturated or unsaturated polyester-based resins but also polyarylate-based resins using aromatic dicarboxylic acids as polymerization components.

[0055] The polyol component (particularly, the diol component) of the polyester resin can be composed of a combination of the xanthene derivative compound and other diol components. Examples of such diol components (or diols) include alkylene glycols (e.g., linear or chain C2-12 alkylene glycols such as ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, tetramethylene glycol, hexanediol, neopentyl glycol, octanediol, and decanediol), (poly)oxyalkylene glycols (e.g., diethylene glycol, triethylene glycol, dipropylene glycol, and C2-4 alkylene glycol), alicyclic diols (e.g., 1,4-cyclohexanediol, Examples of the diols include 1,4-cyclohexanedimethanol, 2,2-bis(4-hydroxycyclohexyl)propane or its alkylene oxide adduct (2,2-bis(4-(2-hydroxyethoxy)cyclohexyl)propane, etc.), aromatic diols (e.g., biphenol, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bisphenol AD, bisphenol F or their alkylene oxide (C2-3 alkylene oxide) adducts (2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, etc.), xylene glycol, etc.). These diols can be used alone or in combination of two or more.

[0056] Preferred diols are linear or chain C2-10 alkylene glycols, particularly C2-6 alkylene glycols (e.g., linear or chain C2-4 alkylene glycols such as ethylene glycol, propylene glycol, and 1,4-butanediol). At least ethylene glycol is often used as the diol. Use of such diols (e.g., ethylene glycol) can improve polymerization reactivity and at the same time impart flexibility to the resin.

[0057] The ratio (molar ratio) of the xanthene derivative compound to the diols (former / latter) may be, for example, about 100 / 0 to 50 / 50, preferably about 100 / 0 to 75 / 25 (e.g., 100 / 0 to 70 / 30), and more preferably about 100 / 0 to 90 / 10 (e.g., 100 / 0 to 80 / 20).

[0058] The diol component may be used in combination with a polyol such as glycerin, trimethylolpropane, trimethylolethane, or pentaerythritol, if necessary.

[0059] Examples of the dicarboxylic acid component constituting the polyester resin include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and derivatives thereof capable of forming esters [e.g., acid anhydrides, acid halides (acid chlorides, etc.), lower alkyl esters (C1-2 alkyl esters, etc.)]. These dicarboxylic acids can be used alone or in combination of two or more.

[0060] Examples of the aliphatic dicarboxylic acid include saturated C3-20 aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and hexadecanedicarboxylic acid (preferably, saturated C3-14 aliphatic dicarboxylic acids, etc.); unsaturated C4-20 aliphatic dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, and mesaconic acid (preferably, unsaturated C4-14 aliphatic dicarboxylic acids, etc.); and derivatives thereof capable of forming esters. In the unsaturated polyester resin, the ratio of the aliphatic unsaturated dicarboxylic acid (maleic acid or its acid anhydride, etc.) may be, for example, about 10 to 100 mol%, preferably 30 to 100 mol%, and more preferably about 50 to 100 mol% (for example, 75 to 100 mol%) relative to the entire dicarboxylic acid component.

[0061] Examples of alicyclic dicarboxylic acids include saturated alicyclic dicarboxylic acids (C3-10 cycloalkane-dicarboxylic acids such as cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and cycloheptanedicarboxylic acid), unsaturated alicyclic dicarboxylic acids (C3-10 cycloalkene dicarboxylic acids such as 1,2-cyclohexenedicarboxylic acid and 1,3-cyclohexenedicarboxylic acid), polycyclic alkane dicarboxylic acids (di- or tricyclic C7-10 alkane-dicarboxylic acids such as bornanedicarboxylic acid, norbornanedicarboxylic acid, and adamantanedicarboxylic acid), polycyclic alkene dicarboxylic acids (di- or tricyclic C7-10 alkene dicarboxylic acids such as bornenedicarboxylic acid and norbornenedicarboxylic acid), and derivatives capable of forming esters thereof.

[0062] Examples of aromatic dicarboxylic acids include aromatic C8-16 dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid (e.g., 2,6-naphthalenedicarboxylic acid), 4,4-diphenyldicarboxylic acid, diphenylether-4,4-dicarboxylic acid, 4,4-diphenylmethanedicarboxylic acid, and 4,4-diphenylketonedicarboxylic acid; and derivatives thereof capable of forming esters.

[0063] The dicarboxylic acid may be used in combination with a polycarboxylic acid such as trimellitic acid or pyromellitic acid, if necessary.

[0064] The dicarboxylic acid component is generally at least one selected from aliphatic dicarboxylic acids and alicyclic dicarboxylic acids, and particularly preferably an aliphatic dicarboxylic acid (a saturated aliphatic dicarboxylic acid or an ester-forming derivative thereof, particularly a saturated C3-14 aliphatic dicarboxylic acid such as adipic acid, suberic acid, sebacic acid, etc.) or an alicyclic dicarboxylic acid (a C5-10 cycloalkane dicarboxylic acid such as cyclohexane dicarboxylic acid).

[0065] As the polyarylate resin, a dicarboxylic acid component containing at least an aromatic dicarboxylic acid is used, and the aromatic dicarboxylic acid can be used in combination with other dicarboxylic acids (aliphatic dicarboxylic acids and / or alicyclic dicarboxylic acids). The ratio of the aromatic dicarboxylic acid to the other dicarboxylic acid may be, for example, the former / latter (molar ratio)=100 / 0 to 10 / 90, preferably 100 / 0 to 30 / 70, more preferably about 100 / 0 to 50 / 50.

[0066] In polyester resins, the ratio (molar ratio) of the dicarboxylic acid component to the polyol component (diol component, such as the above-mentioned xanthene derivative compound) may generally be about the former / latter=1.5 / 1 to 0.7 / 1, preferably about 1.2 / 1 to 0.8 / 1 (particularly, about 1.1 / 1 to 0.9 / 1).

[0067] The weight average molecular weight Mw (polystyrene equivalent) of the polyester resin is not particularly limited, and is, for example, 100 to 50×10 4 , preferably 500 to 30 × 10 4 (For example, 1000 to 20×10 4 ), more preferably 3000 to 30 × 10 4 In the unsaturated polyester resin, the molecular weight per double bond may be about 300 to 1000, preferably about 350 to 800, and more preferably about 400 to 700. The terminal group of the polyester resin may be a hydroxyl group or a carboxyl group, and may be protected by a protecting group as necessary.

[0068] The polyester resin can be produced by a condensation reaction between a polyol component (particularly, a diol component) composed of the xanthene derivative compound and the dicarboxylic acid component by a conventional method, such as a direct polymerization method (direct esterification method) or an ester exchange method.

[0069] (2) Polyurethane resin The polyol component (diol component) constituting the polyurethane resin containing the xanthene derivative compound as a polymerization component (monomer component) may be composed of the xanthene derivative compound alone, or may be used in combination with the diols exemplified in the polyester resin section in addition to the xanthene derivative compound. In addition, a diol component containing the xanthene derivative compound as a constituent unit, for example, a polyester diol produced by reacting a diol component composed of a xanthene derivative compound in which p1=p2=1 in the above chemical formula 1 with a dicarboxylic acid component, or a polyether diol produced by reacting the diol component with an alkylene oxide, can also be used as the diol component of the polyurethane resin. The diol component can also be used alone or in combination of two or more kinds. If necessary, the diol component may be used in combination with a polyol component such as a triol.

[0070] The content of the xanthene derivative compound in the polyol component (diol component) may be, for example, about 10 to 100 mol %, preferably about 20 to 80 mol %, and more preferably about 30 to 70 mol %, based on the entire polyol component (diol component).

[0071] Diisocyanate compounds that constitute polyurethane resins include aromatic diisocyanates [paraphenylene diisocyanate, tolylene diisocyanate (TDI), xylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), naphthalene diisocyanate (NDI), bis(isocyanatophenyl)methane (MDI), toluidine diisocyanate (TODI), 1,2-bis(isocyanatophenyl)ethane, 1,3-bis(isocyanatophenyl)ethane, Examples of the diisocyanate compounds include cyclohexane 1,4-diisocyanate, 1,4-bis(isocyanatophenyl)propane, 1,4-bis(isocyanatophenyl)butane, polymeric MDI, etc., alicyclic diisocyanates [cyclohexane 1,4-diisocyanate, isophorone diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI, etc.], and aliphatic diisocyanates [hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), lysine diisocyanate (LDI), etc.]. These diisocyanate compounds can be used alone or in combination of two or more. These diisocyanate compounds can be used in combination with polyisocyanate compounds (e.g., aliphatic triisocyanates such as 1,6,11-undecane triisocyanate methyl octane and 1,3,6-hexamethylene triisocyanate; triisocyanate compounds such as alicyclic triisocyanates such as bicycloheptane triisocyanate), monoisocyanate compounds (C1-6 alkyl isocyanates such as methyl isocyanate; C5-6 cycloalkyl isocyanates such as cycloalkyl isocyanates; C6-10 aryl isocyanates such as phenyl isocyanate), etc., as needed. The isocyanate compounds also include derivatives such as polymers or modified products of the polyisocyanate compounds.

[0072] The polyurethane resin can be obtained by a conventional method, for example, by carrying out a urethane reaction using 0.7 to 2.5 moles, preferably 0.8 to 2.2 moles, more preferably 0.9 to 2 moles of a diisocyanate component per mole of a polyol component (diol component). If about 0.7 to 1.1 moles of the diisocyanate component are used per mole of the diol component, a thermoplastic resin can be obtained, and if an excess molar amount (for example, about 1.5 to 2.2 moles) of the diisocyanate component is used, a thermosetting resin having a glass isocyanate group at the end can be obtained.

[0073] (3) Polycarbonate resin Examples of polycarbonate-based resins containing the xanthene derivative compound as a polymerization component include polycarbonate-based resins obtained by a conventional method, for example, by reacting a polyol component (particularly, a diol component) composed of at least the xanthene derivative compound (generally, a compound in which p1 = p2 = 1 in the above chemical formula 1) with phosgene (phosgene method), or by reacting a polyol component (diol component) composed of the xanthene derivative compound with a carbonate ester (ester exchange method).

[0074] The polyol component (diol component) may be composed of the xanthene derivative compound alone, or may be composed of the xanthene derivative compound and other diols (diols exemplified in the above polyester resin section, particularly aromatic diols or alicyclic diols). The other diols can be used alone or in combination of two or more. Among the other diols, aromatic diols such as bisphenols such as bisphenol A, AD, and F are particularly preferred. The ratio of the xanthene derivative compound having a hydroxyl group to the diols can be selected from the same range as in the case of the polyester resin.

[0075] The molecular weight of the polycarbonate resin is not particularly limited, and may be, for example, a weight average molecular weight of 1×10 3 ~100×10 4 (For example, 1×10 4 , 100×104 ), preferably 5 × 10 3 ~50×10 4 (For example, 1×10 4 , 50×10 4 ), more preferably 1×10 4 , 25×10 4 (For example, 1×10 4 , 10×10 4 ) degree.

[0076] (4) Epoxy resin The diol or polyol component constituting the epoxy resin may be composed of the xanthene derivative compound alone, or may be composed of a combination of the xanthene derivative compound (generally a compound in which p1=p2=1 in the above chemical formula 1), the polyester resin, and other diols (particularly, aromatic diols or alicyclic diols). The other diols may be used alone or in combination of two or more. Among the diols, aromatic diols such as bisphenols such as bisphenol A, AD, and F are particularly preferred. The ratio of the xanthene derivative compound to the diols may be selected from the same range as in the case of the polyester resin. In addition, the bisphenol xanthene compounds and other diols as necessary may be used in combination with polyols (e.g., phenol novolac).

[0077] The epoxy resin may be obtained by reacting at least the xanthene derivative compound with epichlorohydrin. The weight average molecular weight Mw of the epoxy resin may be, for example, about 300 to 30,000, preferably about 400 to 10,000, and more preferably about 500 to 5,000.

[0078] (5) Vinyl ester resin The vinyl ester resin can be obtained by a conventional method, for example, by reacting the epoxy resin (the epoxy resin containing the xanthene derivative compound) with a polymerizable monomer having at least a carboxyl group (unsaturated monocarboxylic acid). The polymerizable monomer having a carboxyl group may be used in combination with the polyester resin and a dicarboxylic acid (aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, or aromatic dicarboxylic acid (isophthalic acid, terephthalic acid, etc.)) as necessary.

[0079] As the polymerizable monomer having a carboxyl group, an unsaturated monocarboxylic acid can be used. As the unsaturated monocarboxylic acid, generally, (meth)acrylic acid can be used, and cinnamic acid, crotonic acid, sorbic acid, maleic acid monoalkyl ester (monomethyl maleate, etc.) can also be used. These monomers can be used alone or in combination of two or more kinds.

[0080] The amount of the unsaturated monocarboxylic acid used may be about 0.5 to 1.2 mol, preferably about 0.7 to 1.1 mol, and more preferably about 0.8 to 1 mol, per mol of the epoxy group of the epoxy resin.

[0081] The vinyl ester resin can also be obtained by reacting the xanthene derivative compound with glycidyl (meth)acrylate. The amount of glycidyl (meth)acrylate used may be, for example, about 1 to 3 moles, preferably about 1 to 2 moles, per mole of the xanthene derivative compound.

[0082] (6) Acrylic resin The monomer of the acrylic resin can be obtained by reacting the xanthene derivative compound with a polymerizable monomer having a carboxyl group. As the polymerizable monomer having a carboxyl group, generally, an unsaturated monocarboxylic acid, particularly (meth)acrylic acid, can be used, and cinnamic acid, crotonic acid, sorbic acid, maleic acid monoalkyl ester (monomethyl maleate, etc.) and the like can also be used. In place of the unsaturated carboxylic acid, reactive derivatives such as acid chlorides and C1-2 alkyl esters can also be used. These monomers can be used alone or in combination of two or more kinds.

[0083] The acrylic resin may be a homopolymer or copolymer of the (meth)acrylic monomer having the xanthene skeleton, or a copolymer of the (meth)acrylic monomer having the xanthene skeleton and another copolymerizable monomer. The copolymerizable monomer may be either a monofunctional compound or a polyfunctional compound, or a monofunctional compound and a polyfunctional compound may be used in combination. Examples of the copolymerizable monomer include carboxyl group-containing monomers such as (meth)acrylic acid, maleic acid, and maleic anhydride; (meth)acrylic acid esters [(meth)acrylic acid C1-6 alkyl esters such as methyl (meth)acrylate, etc.]; (meth)acrylic acid hydroxyalkyl esters [(meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 3-hydroxypropyl, (meth)acrylic acid 4-hydroxybutyl, etc.]; (meth)acrylonitrile and other vinyl cyanides; styrene and other aromatic vinyl monomers; vinyl carboxylate esters such as vinyl acetate; and ethylene, propylene and other α-olefins.

[0084] These copolymerizable monomers can be used alone or in combination of two or more.

[0085] In addition, a monomer having multiple (meth)acryloyl groups obtained by reacting the xanthene derivative compound with a polymerizable monomer having a carboxyl group may be used as an acrylic resin (i.e., a thermosetting acrylic resin, an oligomer (resin precursor)).

[0086] The resin component (ii) can be produced or prepared by mixing the xanthene derivative compound with a resin (and, if necessary, an additive).

[0087] The mixing method is not particularly limited, and for example, a melt kneading method using a mixer such as a ribbon blender, a tumble mixer, or a Henschel mixer, or a kneading means such as an open roller, a kneader, a Banbury mixer, or an extruder can be used. These mixing methods can be used alone or in combination of two or more kinds.

[0088] The ratio of the xanthene derivative compound in the resin component (ii) may be, for example, about 1 to 80 parts by weight, preferably about 5 to 60 parts by weight, and more preferably about 20 to 60 parts by weight, relative to 100 parts by weight of the resin.

[0089] The resin component may contain an additive, and since the resin component has a xanthene-based skeleton derived from the xanthene derivative compound, the dispersibility of the additive can be improved.

[0090] The additives may be liquid or solid (e.g., powdery solid) at room temperature (e.g., about 15 to 25°C). The additives include fillers or reinforcing agents, colorants (dyes and pigments), conductive agents, flame retardants, plasticizers, lubricants, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), release agents (natural waxes, synthetic waxes, straight-chain fatty acids or metal salts thereof, acid amides, esters, paraffins, etc.), antistatic agents, dispersants, flow control agents, leveling agents, defoamers, surface modifiers (silane coupling agents or titanium-based coupling agents, etc.), stress reducing agents (silicon oils, silicone rubbers, various plastic powders, various high-performance plastic powders, etc.), heat resistance improvers (sulfur compounds, polysilanes, etc.), carbon materials, etc. These additives may be used alone or in combination of two or more.

[0091] Among these additives, preferred are fillers, colorants (dye pigments such as black pigments, red pigments, green pigments, and blue pigments), flame retardants, and carbonaceous materials. Carbonaceous materials that function as fillers, reinforcing agents, colorants, and conductive agents are also preferred.

[0092] Depending on the form (resin pellets, coating composition, etc.), the resin component can be molded into a molded product by a known molding method, for example, injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, coating method (spin coating, roll coating, curtain coating, dip coating, casting molding, etc.), etc. Examples of the shape of the molded product include two-dimensional structures (films, sheets, coating films (or thin films), plates, etc.), and three-dimensional structures (for example, pipes, rods, tubes, leather, hollow products, etc.).

[0093] In another aspect of the present invention, there is provided a polyurethane (co)polymer produced from polymerization components including the xanthene derivative compound according to the aspect of the present invention described above and a diisocyanate compound.

[0094] In this specification, (co)polymer is meant to include both polymer and copolymer, where polymer refers to a homopolymer made of a single repeating unit, and copolymer refers to a composite polymer having two or more types of repeating units.

[0095] In this specification, the term "copolymer" is used to include random (co)polymers, block (co)polymers, graft (co)polymers, and the like.

[0096] In one embodiment of the present invention, the diisocyanate compound contains an isocyanate group and reacts with the hydroxy group of the xanthene derivative compound or an additional diol compound to form a urethane bond.

[0097] The diisocyanate compound is not particularly limited as long as it can be used in the production of polyurethane.

[0098] In one embodiment of the present invention, the diisocyanate compound may be at least one selected from the group consisting of methylene diphenyl diisocyanate (MDI), p-phenylene diisocyanate (PPDI), tolylene-2,4-diisocyanate (2,4-TDI), tolylene-2,6-diisocyanate (2,6-TDI), xylene diisocyanate (XDI), 1,5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), 4,4'-methylene dicyclohexyl diisocyanate (H12MDI), 1,4-cyclohexane diisocyanate (CHDI), isophorone diisocyanate (IPDI), and 1,3-bis(isocyanatomethyl)cyclohexane (H6XDI).

[0099] In yet another aspect of the present invention, there is provided a polycarbonate (co)polymer produced from polymerization components including the xanthene derivative compound according to the above-mentioned aspect of the present invention; and a polycarbonate precursor.

[0100] In one embodiment of the present invention, the polycarbonate precursor is represented by the following chemical formula:

[0101] [ka]

[0102] In the above chemical formula, Rb1 and Rb2 may be the same or different, and each independently represents a halogen group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group, and b1 and b2 are each 0 or 1.

[0103] The polycarbonate precursor plays a role of linking additional comonomers as necessary, and specific examples thereof include phosgene, triphosgene, diphosgene, bromophosgene, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, mK cresyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, and bishaloformates, and any one or a mixture of two or more of these can be used.

[0104] The polymerization may be carried out by either interfacial polymerization or melt polymerization.

[0105] The solvent that can be used in the polymerization is not particularly limited as long as it is a solvent that is used in the polymerization of polycarbonates in the art. For example, halogenated hydrocarbons such as methylene chloride and chlorobenzene can be used.

[0106] The polymerization is preferably carried out in the presence of an acid binder, and examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine.

[0107] In addition, it is preferable to carry out the polymerization in the presence of a molecular weight regulator in order to regulate the molecular weight of the polycarbonate during the polymerization. As the molecular weight regulator, C1-20 alkylphenol can be used, and specific examples thereof include p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, or triacontylphenol. The molecular weight regulator can be added before, during, or after the start of polymerization.

[0108] In addition, in order to accelerate the polymerization reaction, a reaction accelerator such as a tertiary amine compound, a quaternary ammonium compound, or a quaternary phosphonium compound, such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, may be further used.

[0109] According to yet another aspect of the invention, there is provided an optical lens comprising a polymer or copolymer according to one aspect of the invention described above.

[0110] The optical lenses can be manufactured in the desired form by extrusion of the above-mentioned polymers or copolymers, and other processing methods besides extrusion are also applicable.

[0111] In one embodiment of the present invention, the polymer or copolymer that can be used to manufacture the optical lens has high transmittance and high heat resistance, and is therefore easier to process than currently used optical lens materials, making it possible to mass-produce plastic lenses by injection molding. Effect of the Invention

[0112] The present invention relates to a novel high refractive index xanthene monomer having various functional groups, i.e., a novel high refractive index compound having a fluorene and xanthene composite cardo structure and a refractive index of 1.7 or more. The compound of the present invention can be applied to the production of high refractive index optical resins, and the fluorene and xanthene composite cardo structure of the compound has a high glass transition temperature (Tg) with the fluidity of the molecular chains being suppressed as much as possible, so that it can be widely used in the production of high heat resistant resins that require thermal stability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0113] The present invention will be described in more detail below with reference to examples. It will be apparent to those skilled in the art that these examples are merely intended to more specifically illustrate the present invention, and that the scope of the present invention is not limited to these examples according to the gist of the present invention. EXAMPLES

[0114] The method for synthesizing the novel spiro structure compound of the present invention is as follows.

[0115] Production Example 1: Method for producing compound 5 (2,2'-(spiro[fluorene-9,9'-thioxanthene]-2,7-diylbis(oxy))diethanol) (FTX) (1) Synthesis of compound 3 (2,7-dimethoxyspiro[fluorene-9,9'-thioxanthene]) 1) Synthesis of compound 1 (2,7-dimethoxyfluorenone)

[0116] [ka]

[0117] 2) Synthesis of compound 2 ((2-Bromophenyl)thiobenzene)

[0118] [ka]

[0119] 3) Synthesis of compound 3 (2,7-dimethoxyspiro[fluorene-9,9'-thioxanthene])

[0120] [ka]

[0121] 7.857g (29.6mmol) of (2-bromophenyl)thiobenzene was added to a two-neck flask equipped with a thermometer and a stirrer. 15ml of dry THF was added and stirred. After maintaining the temperature at -78℃, 18ml of 1.5M nBuLi was dripped in. Stirred at the same temperature for 1 hour. 5.2g (21.8mmol) of 2,7-dimethoxyfluorene was added to another two-neck flask equipped with a stirrer. 70ml of dry THF was added and stirred, then added to the flask maintained at -78℃ using a syringe. After stirring at the same temperature for 1 hour, the temperature was gradually raised to room temperature and stirred for 3 hours. The reaction solution was decompressed and extracted with chloroform and NaCl. The organic layer was separated and decompressed to obtain solid intermediate 1 (7.69g, 83% yield).

[0122] 17.69g (18mmol) of the intermediate was placed in a two-neck flask equipped with a thermometer, stirrer, and condenser. 70ml of acetic acid and 10ml of 36% HCl were added and stirred at 80°C for 10 hours. The remaining HCl was neutralized with NaHCO3 and water and filtered. The filtered solid was extracted with chloroform and NaHCO3. The organic layer was reduced pressure and purified to obtain solid compound 3 (7.15g, 80% yield).

[0123] (2) Synthesis of Compound 4 and Compound 5 (FTX) 1) Compound 4 (spiro[fluorene-9,9'-thioxanthene]-2,7-diol) synthesis

[0124] [ka]

[0125] 2,7-dimethoxyspiro[fluorene-9,9'-thioxanthene]3g (7.34mmol) was added to a two-neck flask equipped with a thermometer and a stirrer. 60ml (0.12M) of dichloromethane was added and stirred. After the temperature was lowered to 0℃, 22ml (22.02mmol) of dichloromethane containing 1.0M concentration of BBr3 was gradually added dropwise. The mixture was stirred for 3 hours while gradually raising the temperature to room temperature. After the temperature was lowered to 0℃, ice was added to quench the remaining BBr3, and the mixture was extracted with dichloromethane and NaHCO3. The organic layer was separated, reduced pressure, and purified to obtain solid compound 4, spiro[fluorene-9,9'-thioxanthene]-2,7-diol (2.7g, yield 97%, purity 99.8%).

[0126] 2) Compound 5 (2,2'-(spiro[fluorene-9,9'-thioxanthene]-2,7-diylbis(oxy))diethanol) synthesis (FTX synthesis)

[0127] [ka]

[0128] Compound 42.5g (6.57mmol) was added to a three-neck flask equipped with a thermometer, stirrer, and condenser. DMF 13ml was added and stirred. Ethylene carbonate 1ml (15.77mmol) and TBAF (Tetra-n-butylammonium fluoride) 0.2ml (0.2mmol) were added. Stirring was performed at 150℃ for 3 hours. After the reaction was completed, the temperature was lowered to room temperature, and the compound was extracted using chloroform and water. The organic layer was separated, reduced pressure, and purified to obtain solid compound 5, FTX (2,2'-(spiro[fluorene-9,9'-thioxanthene]-2,7-diylbis(oxy))diethanol) (2.83g, yield 92%, purity 99.6%).

[0129] Production example 2: Production method of compound 6 (2,7-bis(2-hydroxyethoxy)spiro[fluorene-9,9'-thioxanthene]10',10'-dioxide) (FTXDO)

[0130] [ka]

[0131] Compound 5, FTX (2,2'-(spiro[fluorene-9,9'-thioxanthene]-2,7-diylbis(oxy))diethanol) 105mg (0.22mmol) was placed in a two-neck flask equipped with a thermometer and stirrer. 7ml (0.03M) of dichloromethane was added and the temperature was lowered to 0℃. At the same temperature, mCPBA (meta-Chloroperoxybenzoic acid) 101mg (0.44mmol) was added. The mixture was gradually warmed to room temperature and stirred for 5 hours.

[0132] After the reaction was completed, the mixture was extracted with dichloromethane and NaHCO3. The organic layer was separated and concentrated. The concentrated solution was purified by column chromatography (eluent: ethyl acetate-hexane) to obtain solid compound 6, FTXDO (2,7-bis(2-hydroxyethoxy)spiro[fluorene-9,9'-thioxanthene]10',10'-dioxide) (83 mg, yield 75%, purity 99.2%).

[0133] Production Example 3: Production method of compound 10 (2,2'-(spiro[fluorene-9,9'-xanthene]-2,7-diylbis(oxy))diethanol) (FX) (1) Synthesis of compound 7 (2,7-dibromospiro[fluorene-9,9'-xanthene])

[0134] [ka]

[0135] 30g (88.76mmol) of 2,7-dibromofluorene and 83g (887.6mmol) of phenol were added to a two-neck flask equipped with a thermometer and a stirrer and stirred. 24ml (355.04mmol) of methanesulfonic acid was added and stirred at 150℃ for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted with chloroform, NaHCO3, and NaCl. The organic layer was separated, reduced pressure, and purified to obtain solid compound 7 (33.28g, yield 76.5%, purity 99.8%).

[0136] (2) Synthesis of compound 8 (2,7-dimethoxyspiro[fluorene-9,9'-xanthene])

[0137] [ka]

[0138] Compound 7 1g (2.039mmol), CuI 1.55g (8.159mmol), and dry DMF 3.3ml were placed in a two-neck flask equipped with a thermometer, stirrer, and condenser and stirred under nitrogen atmosphere. NaOMe 14.7ml (4.6M) was added and refluxed at 120℃ for 24 hours. After the reaction was completed, the mixture was diluted with chloroform and extracted using NH4Cl and water. The organic layer was separated, reduced pressure, and purified to obtain solid compound 8 (0.7g, yield 87%, purity 99.7%).

[0139] (3) Compound 9 (2,7-dihydroxyspiro[fluorene-9,9'-xanthene]) synthesis

[0140] [ka]

[0141] Compound 8 (2 g, 5.096 mmol) was placed in a two-neck flask equipped with a thermometer, stirrer, and condenser, and a nitrogen atmosphere was maintained. Glacial acetic acid (13 ml, 0.4 M) and 47% HBr (2.49 ml, 45.86 mmol) were added, and the mixture was refluxed and stirred at 120°C for 48 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted with chloroform and NaHCO3. The organic layer was separated, reduced pressure, and purified to obtain solid compound 9 (2,7-dihydroxyspiro[fluorene-9,9'-xanthene]) (1.8 g, 97% yield, 99.5% purity).

[0142] (4) Synthesis of compound 10 (2,2'-(spiro[fluorene-9,9'-xanthene]-2,7-diylbis(oxy))diethanol) (FX synthesis)

[0143] [ka]

[0144] Compound 9 (2,7-dihydroxyspiro[fluorene-9,9'-xanthene]) 2g (5.488mmol), dry DMF 13ml, ethylene carbonate 0.887ml (12.07mmol), and TBAF 0.1ml (0.1mmol) were placed in a two-neck flask equipped with a thermometer, stirrer, and condenser, and refluxed at 150°C for 3 hours with stirring. After the reaction was completed, the mixture was cooled to room temperature and extracted using ethyl acetate and water. The organic layer was separated, reduced pressure, and purified to obtain solid compound 10 (2.0g, yield 83.3%, purity 99.3%).

[0145] Example 4: Synthesis of FXAR

[0146] [ka]

[0147] Compound 10 (2,2'-(spiro[fluorene-9,9'-xanthene]-2,7-diylbis(oxy))diethanol) 3.36g (7.4mmol), acrylic acid 1.4mL (18.2mmol), p-toluenesulfonic acid monohydrate 0.37g (1.95mmol), hydroquinone 0.04g (0.34mmol) and dry toluene 20mL were added to a three-neck flask equipped with a thermometer, a stirrer and a condenser, and the mixture was stirred at 120°C for 7 hours. After cooling to room temperature, the compound was extracted with chloroform and an aqueous NaOH solution. The organic layer was separated, reduced pressure and purified to obtain 3.66g of solid compound FXAR (yield 88.0%, purity 99.2%).

[0148] 1 H-NMR (500MHz, CDCl3): δ= 7.52-7.54 (m, 2H), 7.11-7.13 (m, 4H), 6.83-6.84 (d, J = 8.2 Hz, 2H), 6.73 (m, 2H), 6.61 (s, 2H), 6.36-6.37 (d, J = 7.3 Hz, 2H), 6.34 (d, J = 1.5 Hz, 1H), 6.31 (d, J = 1.2 Hz, 1H), 5.99-6.04 (dd, J1= 17.4 Hz, J2= 8.9 Hz, 1H), 5.99-6.04 (dd, J1= 17.4 Hz, J2=11.9 Hz, 1H), 5.73-5.75 (dd, J1= 10.4 Hz, J2= 1.2 Hz, 2H), 4.34-4.35 (t, J = 3.7 Hz, 4H), 4.02 (d, J = 4, 4H).

[0149] Example 5: Synthesis of FTXEP

[0150] [ka]

[0151] In a two-neck flask equipped with a thermometer and stirrer, mix 5.70g (15.0mmol) of compound 4 (spiro[fluorene-9,9'-thioxanthene]-2,7-diol) and 35ml of DMF, slowly add 792mg (33.0mmol) of NaH at room temperature, and stir for 20 minutes. Add 4.17g (45.0mmol) of epichlorohydrin, and stir for 24 hours at room temperature. Add ethyl acetate and water to the reaction mixture to extract the compound. Separate the organic layer, reduce pressure, and purify to obtain 6.29g (yield 85.0%, purity 98.8%) of solid compound FXEP.

[0152] 1 H-NMR (500MHz, CDCl3): δ= 7.57 (d, J = 8.2 Hz, 4H), 7.39 (d, J=7.6 Hz, 4H), 7.25 (s, 1H), 7.14 (t, J=7.6 *2, 4H), 7.08 (m, 2H), 6.92 (dd, J1=8.5Hz, J2= 2.4 Hz, 4H), 6.88(m, 3H),6.54 (m, 4H), 4.1 (m, 4H), 3.84(dd, = 10.8 Hz, J2= 5.6 Hz, 4H), 3.27(m, 4H), 2.83(m, 4H), 2.68(dd, J1=5Hz, J2=2.6Hz, 4H).

[0153] Example 6: Synthesis of FXEP

[0154] [ka]

[0155] In a two-neck flask equipped with a thermometer and stirrer, 3.64g (10.0mmol) of compound 9 (2,7-dihydroxyspiro[fluorene-9,9'-xanthene]) and 25ml of DMF were mixed, and 528mg (22.0mmol) of NaH was gradually added at room temperature, followed by stirring for 20 minutes. 2.78g (30.0mmol) of epichlorohydrin was added, followed by stirring for 24 hours at room temperature. Ethyl acetate and water were added to the reaction mixture to extract the compound, and the organic layer was separated and purified under reduced pressure to obtain 4.10g (yield 86.0%, purity 98.5%) of solid compound FXEP.

[0156] 1 H-NMR (500MHz, CDCl3): δ= 7.52 (m, 2H), 7.19 (d, J = 2.1, 3H), 7.13 (m, 4H), 6.83 (dd, J1 = 8.2 Hz, J2 = 2.1 Hz, 2H), 6.72 (m, 2H), 6.36 (d, J = 7.9 Hz, 2H), 4.02 (m, 2H), 3.76 (m, 2H), 3.19 (s, 2H), 2.6 (m, 2H).

[0157] Production Example 7: Synthesis of FTXAL

[0158] [ka]

[0159] In a three-neck flask equipped with a thermometer, stirrer, and condenser, 3.80g (10.0mmol) of compound 4 (spiro[fluorene-9,9'-thioxanthene]-2,7-diol), 4.42g (32.0mmol) of K2CO3, and 30ml of acetone were added and stirred at room temperature for 10 minutes. The temperature was raised to 65°C, and 2.66g (22mmol) of allyl bromide was added dropwise for 15 minutes, and the mixture was refluxed and stirred for 24 hours. After cooling to room temperature, acetone was distilled, and dichloromethane and water were added to extract the compound. The organic layer was separated, reduced pressure, and purified to obtain 4.15g of solid compound FTXAL (yield 90.0%, purity 99.5%).

[0160] 1 H-NMR (500MHz, CDCl3): δ= 7.49(d, J = 8.5 Hz, 2H), 7.32 (dd, J1 = 7.9 Hz, J2 = 1.2 Hz, 2H), 7.19 (s, 1H), 7.06 (m, 3H), 6.83 (m, 3H), 6.5 (dd, J1 = 8.1 Hz, J2 = 1.1 Hz, 2H), 5.9 (m, 2H), 5.27 (m, 2H), 4.35(m, 3H).

[0161] Example 8: Synthesis of FTXSI

[0162] [ka]

[0163] In a two-neck flask equipped with a thermometer and a stirrer, 5.0 g (10.9 mmol) of FTXAL compound, 4.7 g (23.9 mmol) of 3-mercaptopropyltrimethoxysilane, and 50 ml of THF were placed and stirred at room temperature for 30 minutes. 5 mg of photoinitiator 1-hydroxycyclohexylphenylketone was added, and UV was irradiated at an intensity of 53 mW for 120 seconds, and the reaction solution was stirred for 1 hour. The THF solvent was distilled under reduced pressure, and then EtOAc and water were added to extract the compound. The organic layer was separated, reduced pressure, and purified to obtain 8.15 g of solid compound FTXSI (yield 88.0%, purity 98.8%).

[0164] 1H-NMR (500MHz, CDCl3): δ= 7.57-7.55 (d, J = 8.2 Hz, 2H), 7.4-7.38 (d, J = 7.6 Hz, 2H), 7.15-7.14 (m, 2H), 7.06-7.05 (d, J = 2.4 Hz, 2H), 6.9-6.78 (m, 4H), 6.57-6.55 (d, J = 7.9 Hz, 2H), 3.94-3.92 (m, 4H), 3.75-3.54 (m, 18H), 2.64-2.61 (m, 4H), 2.52-2.49 (m, 4H), 1.99-1.96 (m, 4H), 1.7-1.66 (m, 4H), 0.77-0.71 (m, 4H).

[0165] Production Example 9: Synthesis of FTXAH

[0166] [ka]

[0167] In a two-neck flask equipped with a thermometer and a stirrer, 3.33g (15.8mol) of trimellitic anhydride chloride and 5mL of dry THF are placed and stirred under an argon atmosphere at 0°C. A solution of 2.00g (5.26mmol) of compound 4 (spiro[fluorene-9,9'-thioxanthene]-2,7-diol) and 1.28ml of dry pyridine mixed in 10mL of dry THF is slowly added dropwise, and the mixture is stirred at 0°C for 3 hours. The mixture is then further stirred at room temperature for 24 hours. After filtering the salt produced using hexane, the filtrate is decompressed to distill the solvent. The concentrated solution is recrystallized with acetic anhydride to obtain 3.26g of solid compound FTXAH (yield 85.0%, purity 99.6%).

[0168] 1H-NMR (500MHz, CDCl3): δ= 8.76 (d, J = 0.6 Hz, 2H), 8.65-8.67 (dd, J1 = 7.9 Hz, J2 = 1.2 Hz, 2H), 8.13-8.15 (d, J = 7.9 Hz, 2H), 7.86-7.88 (d, J = 8.2 Hz, 2H), 7.49-7.50 (d, J = 2.1 Hz, 2H), 7.42-7.43 (m, J = 7.9 Hz, 2H), 7.35-7.37 (m, 2H), 7.19-7.22 (t, J = 7.5 Hz, 2H), 6.96-6.99 (m, 2H), 6.64-6.66 (m, J = 7.9 Hz, 2H).

[0169] Example 10: Synthesis of FXAM

[0170] [ka]

[0171] In a three-neck flask equipped with a thermometer, stirrer, and condenser, 1.70g (3.47mmol) of compound 7 (2,7-dibromospiro[fluorene-9,9'-xanthene]), 0.90g (13.88mmol) of sodium azide, 0.52g (4.51mmol) of L-proline, 0.5g (3.47mmol) of Cu2O, and 5ml of DMSO were added and stirred at 100°C for 12 hours under an argon atmosphere. After the reaction solution was cooled to room temperature, 1.5ml of NH4Cl aqueous solution and 5ml of EtOAc were added and stirred for 1 hour. The solid particles were filtered using EtOAc through Celite. The filtrate was extracted with EtOAc and NaHCO3 aqueous solution. The organic layer was separated, reduced pressure, and purified to obtain 1.12g of solid compound FXAM (yield 89.0%, purity 99.0%).

[0172] 1H-NMR (500MHz, DMSO): 7.36-7.37 (d, J = 7.9 Hz, 2H), 7.23-7.24 (m, 4H), 6.87-6.89 (m, 2H), 6.51-6.52 (d, J = 8.2 Hz, 2H), 6.39-6.40 (d, J = 7.6 Hz, 2H), 6.21 (s, 2H), 4.97 (s, 4H).

[0173] Example 11: Synthesis of FTXDOAR

[0174] [ka]

[0175] Compound 6, FTXDO (2,7-bis(2-hydroxyethoxy)spiro[fluorene-9,9'-thioxanthene]10',10'-dioxide) 5.00g (10.0mmol), acrylic acid 1.7mL (24.6mmol), p-toluenesulfonic acid monohydrate 0.50g (2.63mmol), hydroquinone 0.05g (0.46mmol) and dry toluene 30ml were added to a three-neck flask equipped with a thermometer, a stirrer and a condenser, and the mixture was stirred at 120°C for 7 hours. After cooling to room temperature, the compound was extracted with chloroform and an aqueous NaOH solution. The organic layer was separated, reduced pressure and purified to obtain 5.17g of the solid compound FTXDOAR (yield 85.0%, purity 99.7%).

[0176] 1H-NMR (500MHz, CDCl3): δ= 8.15-8.17 (dd, J1 = 8.1 Hz, J2 = 1.1 Hz, 2H), 7.56-7.58 (m, 2H), 7.40-7.43 (m, 2H), 7.22 (m, 4H), 6.89-6.91 (dd, J1 = 8.4 Hz, J2 = 2.3 Hz, 2H), 6.82-6.83 (m, 2H), 6.55-6.57 (m, 2H), 6.30-6.33 (d, J = 1.2 Hz, 2H), 5.98-6.04 (m, 2H), 5.72-5.74 (dd, J1 = 10.5 Hz, J2 = 1.4 Hz, 2H), 4.32-4.34 (m, 4H), 3.99-4.00 (m, 4H).

[0177] Preparation Example 12: Synthesis of 2-hydroxyspiro[fluorene-9,9'-xanthene] (mFXOH)

[0178] [ka]

[0179] 10 g (50.96 mmol) of 2-hydroxy-9-fluorene and 23.9 g (254.8 mmol) of phenol were added to a three-neck flask equipped with a thermometer, a stirrer, and a condenser. Then, 9.0 mL (142.7 mmol) of methanesulfonic acid was added, and the reaction mixture was stirred at 150 °C for 3 hours. When the reaction was complete, the compound was extracted with ethyl acetate and aqueous NaHCO3 after cooling to room temperature. The organic layer was separated, decompressed, and purified to obtain 13.9 g (78.3% yield, 99.7% purity) of the solid compound, 2-hydroxyspiro[fluorene-9,9'-xanthene](FXmOH).

[0180] 1H-NMR (500MHz, CDCl3): δ= 7.62-7.55 (m, 2H), 7.27-7.23 (m, 1H), 7.14-7.09 (m, 4H), 7.06-7.03 (m, 2H), 6.76-6.74 (dd, J = 8.2 Hz, 1.8 Hz, 1H), 6.71-6.69 (t, 2H), 6.52 (s, 1H), 6.36-6.35 (d, J = 7.6 Hz, 2H), 4.82 (s, 1H). Example 13: Synthesis of mFX

[0181] [ka]

[0182] In a three-neck flask equipped with a thermometer, stirrer, and condenser, 4 g (11.5 mmol) of mFXOH was dissolved in 15 ml of DMF, and 0.836 mL (12.6 mmol) of ethylene carbonate and 0.1 mL (0.1 mmol) of TBAF were added to the solution and stirred at 150°C for 2 hours. After the reaction was completed, the temperature was lowered to room temperature and the mixture was extracted with ethyl acetate. The organic layer was separated and distilled, and then crystallized with ethyl acetate and hexane to obtain 4.47 g (yield 99.3%, purity 99.7%) of white solid compound mFX.

[0183] 1 H-NMR (500MHz, CDCl3): δ= 7.63-7.61 (dd, J = 7.9 Hz, 3.4 Hz, 2H), 7.27-7.23 (m, 1H), 7.15-7.10 (m, 4H), 7.07-7.04 (m, 2H), 6.86-6.84 (dd, J = 8.4 Hz, 2.3 Hz, 1H), 6.72-6.69 (m, 2H), 6.64-6.63 (d, J = 2.4 Hz, 1H), 6.36-6.34 (dd, J = 7.8 Hz, 1.4 Hz, 2H), 3.89-3.88 (m, 2H), 3.78-3.77 (d, J = 4 Hz, 2H).

[0184] Example 14: Synthesis of mFXAR

[0185] [ka]

[0186] In a three-neck flask equipped with a thermometer, stirrer, and condenser, 2 g (5.1 mmol) of mFX, 0.64 mL (7.65 mmol) of m-acrylic acid, and 10 mL of toluene were placed. Next, 0.1 g of p-toluenesulfonic acid monohydrate was placed and heated and stirred at 100°C for 4 hours. After the reaction was completed, the temperature was lowered to room temperature, and the mixture was extracted with chloroform. The organic layer was separated and distilled, and then recrystallized with ethyl acetate and hexane to obtain 1.92 g of white solid compound mFXAR (yield 82.2%, purity 99.8%).

[0187] 1 H-NMR (500MHz, CDCl3): δ= 7.63-7.61 (dd, J = 7.9 Hz, 2.1 Hz, 2H), 7.28-7.25 (t, 1H), 7.15-7.11 (m, 4H), 7.07-7.04 (m, 2H), 6.87-6.85 (m, 1H), 6.72-6.69 (m, 2H), 6.64-6.63 (m, 1H), 6.36-6.34 (d, J = 7.9 Hz, 2H), 6.01 (s, 1H), 5.46-5.45 (d, J = 1.2 Hz, 1H), 4.33-4.31 (m, 2H), 4.03-4.01 (m, 2H), 2.93 (s, 3H).

[0188] Preparation Example 15: Synthesis of Compounds 4, 13, and 15

[0189] [ka]

[0190] Synthesis of compounds 4, 13, and 15 In a three-neck flask equipped with a thermometer, stirrer, and condenser, 6g / 6.18g / 6.61g (12.6mmol) of compounds 3-1 / 3-2 / 3-3, respectively, 1.82g (25.3mmol), 0.016g (0.12mmol) of 4-methoxyphenol, 0.025g (0.12mmol) of tetraethylammonium bromide, and 25g of cyclopentanone were mixed. The mixture was stirred at 120°C for 5 hours and then cooled to room temperature. Ethyl acetate and water were added to the reaction mixture to extract the compounds. The organic layer was separated, reduced pressure, and purified to obtain 7.19g / 7.21g / 7.41g of solid compounds 4 / 13 / 15, respectively (yields 92.0% / 90% / 88.0%, purity 98.5% / 98.7% / 98.8%).

[0191] <Compound 4 NMR> 1 H NMR (500 MHz, CDCl3) δ 7.60 (d, 2H), 7.22-7.17 (m, 4H), 6.90 (dd, 2H), 6.81-6.76 (m, 2H), 6.67 (d, 2H), 6.44-6.39 (m, 4H), 6.15-6.09 (m, 2H), 5.84 (dd, 2H) 4.31-4.27 (m, 4H), 4.20-4.17 (m, 2H), 3.94-3.90 (m, 4H), 3.75 (s, 2H); <Compound 13 NMR> 1 H NMR (500 MHz, CDCl3) δ 7.76 (d, 2H), 7.55 (d, 2H), 7.22-7.17 (m, 2H), 6.90 (dd, 2H), 6.81 (s, 2H), 6.67 (d, 2H), 6.44-6.39 (m, 4H), 6.15-6.09 (m, 2H), 5.84 (dd, 2H) 4.31-4.27 (m, 4H), 4.20-4.17 (m, 2H), 3.94-3.90 (m, 4H), 3.75 (s, 2H); <Compound 15 NMR> 1H NMR (500 MHz, CDCl3) δ 7.76 (d, 2H), 7.62 (d, 2H), 7.33-7.30 (m, 2H), 7.06 (dd, 2H), 6.86 (s, 2H), 6.70 (d, 2H), 6.44-6.39 (m, 4H), 6.15-6.09 (m, 2H), 5.84 (dd, 2H) 4.31-4.27 (m, 4H), 4.20-4.17 (m, 2H), 3.94-3.90 (m, 4H), 3.75 (s, 2H).

[0192] Preparation Example 16: Synthesis of Compounds 6, 8, 10, and 16

[0193] [ka]

[0194] Synthesis of compounds 6, 8, 10, and 16 Into a three-neck flask equipped with a thermometer, a stirrer, and a condenser, 6.20 g / 6.68 g (10 mmol) of compound 4 / 15, PGMEA (propylene glycol monomethyl ether acetate) (amounts such that the ratio of the total mass of compound 4 / 15 and compound 5 / 7 / 9 to the total mass of compound 4 / 15, compound 5 / 7 / 9, and PGMEA is 68%), 3.08 g / 3.76 g / 2.96 g (20 mmol) of compound 5 / 7 / 9, 0.001 g (0.032 mmol), and 0.026 g (0.1 mmol) of triphenylphosphine are added. At this time, the PGMEA was added in an amount such that the mass ratio of (compound 4+compound 5) / (compound 4+compound 5+PGMEA), (compound 4+compound 7) / (compound 4+compound 7+PGMEA), (compound 4+compound 9) / (compound 4+compound 9+PGMEA), or (compound 15+compound 9) / (compound 15+compound 9+PGMEA) was 68%.

[0195] The mixture was stirred at 120°C for 2 hours and then at 70°C for 4 hours. Ethyl acetate and water were added to the reaction mixture to extract the compounds. The organic layer was separated, decompressed, and purified to obtain solid compounds 6, 8, 10, and 16 in amounts of 8.47g / 8.77g / 7.61g / 8.58g (yields 85.0% / 88% / 83% / 90%, purities 98.7% / 98.6% / 99.0% / 99.2%), respectively.

[0196] <Compound 6 NMR> 1 H NMR (500 MHz, CDCl3) δ 11.00 (s, 2H), 8.13 (d. 2H), 7.59 (d, 2H), 7.39 (d, 2H), 7.22-7.17 (m, 4H), 6.85-6.81 (m, 2H), 6.81-6.77 (m, 2H), 6.66 (d, 2H), 6.43 (d, 2H), 6.27 (dd, 2H), 6.05 (m, 2H), 5.59 (dd, 2H), 5.06 (m, 2H), 4.70-4.66 (m, 4H), 4.45-4.41 (m, 4H), <Compound 8 NMR> 1 H NMR (500 MHz, CDCl3) δ 11.00 (s, 2H), 7.59 (d, 2H), 7.22-7.17 (m, 4H), 6.91-6.98 (m, 2H), 6.81-6.77 (m, 2H), 6.66 (d, 2H), 6.43 (d, 2H), 6.27 (dd, 2H), 6.05 (m, 2H), 5.59 (dd, 2H), 5.06 (m, 2H), 4.51-4.46 (m, 4H), 4.23-4.18 (m, 4H), 3.54 (s, 8H), <Compound 10 NMR> 1H NMR (500 MHz, CDCl3) δ 11.00 (s, 2H), 8.32-8.28 (m, 4H), 7.92-7.88 (m, 4H), 7.59 (d, 2H), 7.22-7.17 (m, 4H), 6.86-6.81 (m, 2H), 6.81-6.78 (m, 2H), 6.66 (d, 2H), 6.43 (d, 2H), 6.27 (dd, 2H), 6.05 (m, 2H), 5.59 (dd, 2H), 5.06 (m, 2H), 4.70-4.66 (m, 4H), 4.45-4.21 (m, 4H), <NMR of Compound 16> 1 H NMR (500 MHz, CDCl3) δ 11.00 (s, 2H), 8.32-8.28 (m, 4H), 7.90-7.86 (m, 4H), 7.76 (d, 2H), 7.68-7.63 (m, 4H), 7.33-7.28 (m, 2H), 6.81-6.77 (m, 2H), 6.66 (d, 2H), 6.43 (d, 2H), 6.27 (dd, 2H), 6.05 (m, 2H), 5.59 (dd, 2H), 5.06 (m, 2H), 4.70-4.66 (m, 4H), 4.45-4.41 (m, 4H).

[0197] Production Example 17: Synthesis of Compounds 12 and 14 Synthesis of compounds 12,14

[0198]

change

[0199] In a three-neck flask equipped with a thermometer, a stirrer, and a condenser, 6.20g / 6.36g (10mmol) of compound 4 / 13, cyclopentanone (amount so that the ratio of the total mass of compound 4 / 13 and compound 11 to the total mass of compound 4 / 13, compound 11, and cyclopentanone is 50%), 2.97g (15mmol) of compound 11, 0.001g (0.032mmol) of 4-methoxyphenol, and 0.026g (0.1mmol) of triphenylphosphine are added. At this time, the cyclopentanone was added in an amount such that the mass ratio of (compound 4 + compound 11) / (compound 4 + compound 11 + cyclopentanone) and (compound 13 + compound 11) / (compound 13 + compound 11 + cyclopentanone) was 50%.

[0200] The mixture was stirred at 120°C for 2 hours and then at 70°C for 6 hours. Ethyl acetate and water were added to the reaction mixture to extract the compounds. The organic layer was separated, reduced pressure, and purified to obtain solid compounds 12 and 14 (8.54g / 8.88g, yields 84.0% and 86%, purity 98.6% / 99.1%), respectively.

[0201] <Compound 12 NMR> 1 H NMR (500 MHz, CDCl3) δ 11.00 (bs, 2H), 8.83 (s, 2H), 8.75 (s, 2H), 8.17-8.13 (m, 4H), 7.74-7.70 (m, 4H), 7.59 (d, 2H), 7.22-7.17 (m, 4H), 6.91-6.87 (m, 2H), 6.81-6.77 (m, 2H), 6.66 (d, 2H), 6.43 (d, 2H), 6.27 (dd, 2H), 6.05 (m, 2H), 5.59 (dd, 2H), 5.06 (m, 2H), 4.70-4.65 (m, 4H), 4.30-4.24 (m, 4H) <Compound 14 NMR> 1H NMR (500 MHz, CDCl3) δ 11.00 (bs, 2H), 8.83 (s, 2H), 8.75 (s, 2H), 8.17-8.12 (m, 4H), 7.74-7.70 (m, 4H), 7.66 (d, 2H), 7.42-7.38 (m, 4H), 7.03-6.91 (m, 2H), 6.81-6.77 (m, 2H), 6.66 (d, 2H), 6.43 (d, 2H), 6.27 (dd, 2H), 6.05 (m, 2H), 5.59 (dd, 2H), 5.06 (m, 2H), 4.69-4.65 (m, 4H), 4.44-4.40 (m, 4H).

[0202] Production Example 18: Synthesis of Compound FXAH [FXAH manufacturing method]

[0203] [ka]

[0204] In a two-neck flask equipped with a thermometer and a stirrer, 8.66 g (41.2 mmol) of trimellitic anhydride chloride and 20 mL of dry THF were placed and stirred at 0°C under an argon atmosphere. A solution of 5.0 g (13.7 mmol) of FX, 3.3 ml of dry pyridine, and 22 ml of dry THF was slowly added dropwise, and the mixture was stirred at 0°C for 3 hours. The mixture was then further stirred at room temperature for 24 hours. After filtering the salt produced using hexane, the filtrate was decompressed to distill the solvent. The concentrated solution was recrystallized with acetic anhydride to obtain 8.0 g of solid compound FXAH (yield 82.0%, purity 99.0%).

[0205] 1 H NMR (CDC13, 500 MHz, ppm): 8.57 (d, 2H), 8.56 (s, 2H), 8.44 (d, 2H), 7.94 (d, 2H), 7.44 (d, 2H), 7.27 (dd, 2H), 7.22 (dd, 2H), 7.21 (d, 2H), 7.19 (d, 2H), 7.05 (dd, 2H).

[0206] Production Example 19: Synthesis of Compounds FXAHAR and FTXAHAR [FXAHAR / FTXAHAR manufacturing method]

[0207] [ka]

[0208] In a three-neck flask equipped with a thermometer, stirrer, and condenser, 7.1g / 7.3g (10.0mmol) of FXAH / FTXAH, 2.32g / 2.60g (20.0mmol) of 2-hydroxyethyl acrylate / 2-hydroxyethyl methacrylate, 0.013g (0.10mmol) of 4-methoxyphenol, 0.021g (0.10mmol) of tetraethylammonium bromide, and 30g of cyclopentanone were mixed. The mixture was stirred at 120°C for 6 hours and then cooled to room temperature. Ethyl acetate and water were added to the reaction mixture to extract the compound. The organic layer was separated, reduced pressure, and purified to obtain 8.0g / 7.9g of solid compounds FXAHAR / FTXAHAR, respectively (yield 85.0% / 82%, purity 98.9% / 99.0%).

[0209] <Compound FXAHAR NMR> 1 H NMR (CDC13, 500 MHz, ppm): 1 H NMR (CDC13, 500 MHz, ppm): 11.00 (s, 2H), 8.45 (s, 2H), 8.41 (d, 2H), 8.34 (d, 2H), 7.94 (d, 2H), 7.44 (s, 2H), 7.27 (d, 2H), 7.22 (dd, 2H), 7.21 (d, 2H), 7.19 (d, 2H), 7.05 (dd, 2H), 6.27 (s, 2H), 6.06 (s, 2H), 5.59 (s, 2H), 4.56 (d, 4H), 4.48 (d, 4H). <Compound FTXAHAR NMR> 1<h2 style=";text-align:left;direction:ltr">H NMR (CDC13, 500 MHz, ppm): IH NMR (CDC13, 500 MHz, ppm): 11.00 (s, 2H), 8.46 (s, 2H), 8.41 (d, 2H), 8.34 (d, 2H), 7.94 (d, 2H), 7.65 (d, 2H), 7.44 (s, 2H), 7.33 (dd, 2H), 7.27 (d, 2H), 7.07 (dd, 2H), 7.03 (d, 2H), 6.48 (s, 2H), 6.40 (s, 2H), 4.56 (d, 4H), 4.48 (d, 4H), 2.01 (s, 6H).

Claims

1. A compound represented by the following chemical formula 1: [Formula 1] In the above formula 1, X, R １ａ , R １ｂ , R ２ａ , and R ２ｂ represents a substituent; X is O, S, or SO ２ and k1 and k2 independently represent an integer of 0 to 4; p1 and p2 independently represent an integer of 0 to 4 (provided that p1 + p2 is an integer of 1 to 8); R ２ａ , and R ２ｂ are independently H, linear or branched C １－１０ Alkyl, linear or branched C １－１０ Alkoxy, C １－１０ Hydroxyalkoxy, C １－１０ Alkoxy (C １－１０ ) Alkoxy, phenyl, C １－１０ Alkoxyphenyl, halogen, amino, C １－５ Haloalkyl, C １－５ Alkylamino, C １－５ Dialkylamino, arylamino, diarylamine, aryl C １－５ represents an alkylamino or cyclic amino group; R １ａ and R １ｂ are each selected from the substituents represented by the following chemical formulas 2-1 to 2-17, [Case 2] [ka] [ka]

2. The R ２ａ , and R ２ｂ are independently H or C １ ~C ４ and k1 and k2 are independently 0 or 1.

3. The compound according to claim 1 , wherein p1 and p2 are each independently 0 or 1.

4. The compound according to claim 1, which is represented by any one of the following chemical formulas 3-1 to 3-16: [C3] [ka] [ka]

5. The compound according to any one of claims 1 to 4, characterized in that X is O.

6. The compound according to claim 5, which is represented by any one of the following chemical formulas 4-1 to 4-10: [C4] [ka] [ka]

7. The compound according to claim 5, which is represented by any one of the following chemical formulas 4-13 to 4-18: [C5]

8. A compound according to any one of claims 1 to 4, characterised in that X is S.

9. The compound according to claim 8, which is represented by any one of the following chemical formulas 5-1 to 5-9: [C6] [ka]

10. The compound according to claim 8, which is represented by any one of the following chemical formulas 5-10 to 5-13: [C7]

11. X is SO ２ The compound according to any one of claims 1 to 4, characterized in that

12. The compound according to claim 11, which is represented by any one of the following chemical formulas 6-1 to 6-5: [C8]

13. The compound according to claim 11, represented by the following chemical formula 6-6: [C9]

Images